U.S. patent number 7,560,493 [Application Number 10/304,860] was granted by the patent office on 2009-07-14 for cosmetic and/or dermatological composition containing at least one oxidation-sensitive hydrophilic active principle and at least one n-vinylimidazole polymer or copolymer.
This patent grant is currently assigned to L'Oreal. Invention is credited to Bruno Biatry, Eric Lheureux.
United States Patent |
7,560,493 |
Biatry , et al. |
July 14, 2009 |
**Please see images for:
( Certificate of Correction ) ** |
Cosmetic and/or dermatological composition containing at least one
oxidation-sensitive hydrophilic active principle and at least one
N-vinylimidazole polymer or copolymer
Abstract
The invention relates to a composition for topical use
containing, in a physiologically acceptable medium having an
aqueous phase, at least one oxidation-sensitive hydrophilic active
principle and at least one non-crosslinked N-vinylimidazole polymer
or copolymer, the active principle and the said polymer or
copolymer both being in the aqueous phase.
Inventors: |
Biatry; Bruno (Vincennes,
FR), Lheureux; Eric (Montgerno, FR) |
Assignee: |
L'Oreal (Paris,
FR)
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Family
ID: |
8869872 |
Appl.
No.: |
10/304,860 |
Filed: |
November 27, 2002 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20030143275 A1 |
Jul 31, 2003 |
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Foreign Application Priority Data
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Nov 28, 2001 [FR] |
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01 15375 |
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Current U.S.
Class: |
514/772.7;
514/772.4; 514/772.2; 514/772; 424/400 |
Current CPC
Class: |
A61Q
19/02 (20130101); A61P 17/16 (20180101); A61K
8/676 (20130101); A61P 17/00 (20180101); A61Q
5/08 (20130101); A61P 43/00 (20180101); A61Q
19/08 (20130101); A61K 8/817 (20130101); A61K
2800/522 (20130101) |
Current International
Class: |
A61K
47/34 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 282 951 |
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Sep 1988 |
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EP |
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0 380 367 |
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Aug 1990 |
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EP |
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1 133 974 |
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Sep 2001 |
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EP |
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Other References
Sigma-Aldrich BioChemika Ultra disclosure, downloaded from the
world wide web on Jul. 19, 2007. cited by examiner .
ACS News "Chemistry Grads Post Gains in 2005", Chemical and
Engineering News, Jul. 24, 2006. cited by examiner .
Franchi, Jocelyne, et al., Depigmenting Effects of Calcuium
D-Panthetheine S-Sulfonate on Human Melanocytes, Jun. 2000, Pigment
Cell Research, vol. 13, p. 165. cited by other .
Zreik, et al., Molecular Human Reproduction 1999, 5(4), 299-302.
cited by other.
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Primary Examiner: Silverman; Eric E.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt, P.C.
Claims
The invention claimed is:
1. A composition comprising: a physiologically acceptable medium
comprising an aqueous phase; at least one oxidation-sensitive
hydrophilic active principle, wherein the hydrophilic active
principle is selected from the group consisting of ascorbic acid,
5,6-di-O-dimethylsilylascorbate, dl-.alpha.-tocopheryl di-ascorbyl
phosphate potassium salt, magnesium ascorbyl phosphate, sodium
ascorbyl phosphate phloroglucinol, kojic acid, and mixtures
thereof; and at least one non-crosslinked
N-vinylimidazole/N-vinylpyrrolidone copolymer, the at least one
active principle and the at least one
non-crosslinked-N-vinylimidazole/N-vinylpyrrolidone copolymer both
being present in the aqueous phase, wherein the copolymer is
present in concentration of between 0.1 and 5% by weight of the
aqueous phase and wherein no more than 30% of the
oxidation-sensitive hydrophilic active principle in the composition
is decomposed after 2 months at 45.degree. C.
2. A composition according to claim 1, wherein the
oxidation-sensitive hydrophilic active principle is ascorbic
acid.
3. A composition according to claim 1, comprising a non-crosslinked
copolymer selected from the group consisting of a
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 1 200 000 and a
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 10 000.
4. A composition according to claim 1, wherein the molar ratio of
the N-vinylimidazole unit equivalent to the oxidation-sensitive
hydrophilic active principle is from 0.004 to 16.
5. A composition according to claim 4, wherein the molar ratio of
the N-vinylimidazole unit equivalent to the oxidation-sensitive
hydrophilic active principle is from 0.01 to 1.
6. A composition according to claim 1, wherein the copolymer is
present in a concentration of between 0.1 and 2% by weight of the
aqueous phase.
7. A composition according to claim 1, wherein the copolymer has a
molar fraction of N-vinylimidazole units of from 0.1 to 1.
8. A composition according to claim 7, wherein the copolymer has a
molar fraction of N-vinylimidazole units of from 0.4 to 0.9.
9. A composition according to claim 1, wherein the active
priciniple is selected from the group consisting of
5,6-di-O-dimethylsilylascorbate, dl-.alpha.-tocopheryl di-ascorbyl
phosphate potassium salt, magnesium ascorbyl phosphate, sodium
ascorbyl phosphate phioroglucinol, and mixtures thereof.
10. A method of stabilizing an oxidation-sensitive hydrophilic
active principle in an aqueous medium, comprising adding thereto a
stabilizing amount of a non-crosslinked
N-vinylimidazole/N-vinylpyrrolidone copolymer, wherein the
hydrophilic active principle is selected from the group consisting
of ascorbic acid, 5,6-di-O-dimethylsilylascorbate, dl-a-tocopheryl
di-ascorbyl phosphate potassium salt, magnesium ascorbyl phosphate,
sodium ascorbyl phosphate phioroglucinol, kojic acid, and mixtures
thereof.
11. The method according to claim 10, wherein the non-crosslinked
copolymer is selected from the group consisting of a
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 1 200 000 and a
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 10 000.
12. The method according to claim 10, wherein the
oxidation-sensitive hydrophilic active principle is ascorbic
acid.
13. The composition according to claim 1, wherein no more than 25%
of the oxidation-sensitive hydrophilic active principle in the
composition is decomposed after 2 months at 45.degree. C.
14. method of treating skin comprising applying the composition
according to claim 1 to skin.
Description
FIELD OF THE INVENTION
The present invention relates to a composition comprising at least
one oxidation-sensitive hydrophilic active principle and at least
one N-vinylimidazole polymer or copolymer. Preferably the
composition is a cosmetic and/or dermatological composition. Also,
preferably, the composition comprises a physiologically acceptable
medium comprising an aqueous phase.
BACKGROUND OF THE INVENTION
It is known to introduce, into cosmetic compositions, various
active principles intended to contribute specific treatments to the
skin and/or hair. However, some of these active principles exhibit
the disadvantage of being unstable in an aqueous medium and of
easily decomposing on contact with water, in particular because of
oxidation phenomena. They thus rapidly lose their activity over
time and this instability conflicts with the desired
effectiveness.
Attempts have thus been made for a long time to formulate ascorbic
acid or vitamin C because of its numerous beneficial properties. In
particular, ascorbic acid stimulates the synthesis of the
connective tissue and in particular of collagen, strengthens the
defenses of the cutaneous tissue against external attacks, such as
ultraviolet radiation and pollution, compensates for vitamin E
deficiency of the skin, depigments the skin and has a role in
combatting free radicals. These last two properties make it an
excellent candidate as cosmetic or dermatological active principle
for combatting ageing of the skin or for preventing ageing of the
skin. Unfortunately, because of its chemical structure (of
.alpha.-ketolactone), ascorbic acid is highly sensitive to certain
environmental parameters and in particular to oxidation phenomena.
There thus ensues rapid decomposition of formulated ascorbic acid
in the presence of these parameters and in particular in the
presence of oxygen, light or metal ions, as a function of the
temperature or under certain pH conditions (Pharm. Acta. Helv.,
1969, 44, 611-667; STP Pharma, 1985, 4, 281-286).
Several solutions have thus been envisaged in the prior art for
reducing and/or slowing down the decomposition of ascorbic
acid.
Provision has thus been made to use ascorbic acid in the form of a
chemical derivative (magnesium ascorbyl phosphate or esters of
fatty acids and ascorbic acid), but the bioavailability of these
derivatives is very low (J. Am. Acad. Dermatol., 1996, 34,
29-33).
The instability of ascorbic acid with respect to oxygen can be
improved by using specific packagings, such as twin compartments
under an inert atmosphere, as disclosed in U.S. Pat. No. 5,935,584,
or alternatively by the use of two-phase emulsions, one phase of
which is composed of a dry powder comprising ascorbic acid and the
second phase of which is a liquid phase. The mixing of the two
phases has to be carried out at the time of use (WO 98/43598).
These solutions have disadvantages with regard to the cost and the
complexity of the manufacturing operations and significant
restrictions with regard to use.
Another solution provided in the prior art consists in using a high
concentration of glycols or polyols in order to reduce the
solubility of oxygen in the formulation, thus protecting the
ascorbic acid (WO 96/24325, EP 0 755 674, U.S. Pat. No. 5,981,578).
The polyols can optionally be incorporated in liposomes, as
disclosed in U.S. Pat. No. 6,020,367. However, these solutions
exhibit the disadvantage of resulting in sticky formulations, the
cosmetic quality of which is difficult to improve. Furthermore, the
presence of a high concentration of these compounds can lead to
phenomena of irritation.
Ascorbic acid can also be formulated in anhydrous media, such as
silicones (U.S. Pat. No. 6,194,452), which are capable of creating
an anhydrous barrier around ascorbic acid. A major disadvantage of
such solutions results from the lack of freshness on
application.
The need thus remains for a composition employable in particular in
the cosmetics field, in which a hydrophilic active principle which
is unstable in an oxidizing medium is stabilized, which is
comfortable on application, which does not lead to any skin
irritation after application and which is compatible with the
constraints of an industrial implementation of its manufacturing
process.
OBJECTS OF THE INVENTION
One object of the present invention is to provide a composition
comprising an oxidation-sensitive active principle, which
preferably exhibits good cosmetic properties, both with regard to
touch and with regard to tolerance, and the preservation of which
over time does not require specific precautions.
SUMMARY OF THE INVENTION
The inventors have discovered that the use of non-crosslinked
N-vinylimidazole polymers or copolymers in compositions in which
the aqueous phase includes an oxidation-sensitive active principle,
such as ascorbic acid, makes it possible to achieve the
abovementioned object.
In the prior art, some compounds having an imidazole structure have
been disclosed for their stabilizing properties. Thus, in Patent
Application EP 0 586 106, several imidazole-based molecules are
used to stabilize certain retinoids against chemical decomposition.
Furthermore, polymeric emulsifiers composed of N-vinylimidazole, of
alkyl acrylates and of vinyl acetates are disclosed in U.S. Pat.
No. 4,057,622. They are used for the purpose of replacing known
emulsifiers in order to overcome their disadvantages, in particular
with regard to smell, and to stabilize water-in-oil emulsions.
Finally, N-vinylimidazole/N-vinylcaprolactam/N-vinylpyrrolidone
copolymers are disclosed in U.S. Pat. No. 6,191,188. They are used
in the manufacture of hair-strengthening compositions.
To the knowledge of the inventors, polymers or copolymers
comprising N-vinylimidazole units have never been used in
combination with hydrophilic active principles sensitive to
decomposition by oxidation for the purpose of improving their
stability in an aqueous medium. This is true in particular in the
case of ascorbic acid.
An embodiment of the present invention is therefore a composition
preferably for topical use comprising, preferably in a
physiologically acceptable medium comprising an aqueous phase, at
least one oxidation-sensitive hydrophilic active principle and at
least one non-crosslinked N-vinylimidazole polymer or copolymer,
the at least one active principle and the at least one polymer or
copolymer both being present in the aqueous phase. The copolymer is
generally preferably present in an amount sufficient to stabilize
the oxidation-sensitive hydrophilic active principle.
The invention also relates to the use of a non-crosslinked
N-vinylimidazole polymer or copolymer to stabilize an
oxidation-sensitive hydrophilic active principle in an aqueous
medium.
According to the invention, the term "hydrophilic active principle"
is understood to mean a compound having a solubility in water of at
least 0.25% at ambient temperature (25.degree. C.).
According to the invention, the term "oxidation-sensitive
hydrophilic active principle" is understood to mean any active
principle of natural or synthetic origin capable of undergoing
decomposition by an oxidation mechanism. This oxidation phenomenon
can have several causes, in particular the presence of oxygen, of
light or of metal ions, a high temperature or certain pH
conditions.
Mention may be made, by way of example and without implied
limitation, of: ascorbic acid and its derivatives, such as salts or
esters thereof, particularly the 5,6-di-O-dimethylsilylascorbate
(sold by Exsymol under the reference PRO-AA), the potassium salt of
dl-.alpha.-tocopheryl dl-ascorbyl phosphate (sold by Senju
Pharmaceutical under the reference SEPIVITAL EPC), magnesium
ascorbyl phosphate or sodium ascorbyl phosphate (sold by Roche
under the reference Stay-C 50). Mention may also be made of active
principles, such as phloroglucinol and kojic acid.
Among oxidation-sensitive hydrophilic active principles, ascorbic
acid is more particularly preferred.
The oxidation-sensitive hydrophilic active principle may be present
in any amount, preferably that amount sufficient to bring about its
desired effect(s). Examples include 0.5, 1, 5, 15 and 25 grams per
100 grams of composition.
According to the invention, the term "non-crosslinked
N-vinylimidazole polymer or copolymer" is understood to mean any
polymer comprising N-vinylimidazole units and not comprising a
crosslinking agent. Copolymers suitable for the implementation of
the invention are, for example, copolymers combining
N-vinylimidazole, with N-vinylpyrrolidone and/or N-vinylcaprolactam
subunits.
In an advantageous aspect of the invention, the copolymer has a
molar fraction of N-vinylimidazole units of between 0.1 and 1, more
preferably between 0.4 and 0.9.
According to another advantageous aspect of the invention, the
molar ratio of the N-vinylimidazole unit equivalent to the
oxidation-sensitive hydrophilic active principle varies between
0.004 and 16 and preferably between 0.01 and 1.
Use will preferably be made of an
N-vinylimidazole/N-vinylpyrrolidone copolymer.
The weight-average molar mass of the N-vinylimidazole polymers will
advantageously be between 1 000 and 1.times.10.sup.7 and preferably
between 5 000 and 5.times.10.sup.6.
Use may be made, to this end, of the
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 1 200 000 sold under the reference
LUVITEC VPI 55K72W by BASF or the vinylpyrrolidone/vinylimidazole
(50/50) copolymer having a weight-average molar mass of 10 000 sold
under the reference LUVITEC VPI 55K18P by BASF. The polymers or
copolymers according to the invention can, for example, be prepared
according to the method disclosed in Patent Application
WO-97/45517.
The at least one polymer or copolymer is preferably present in the
composition according to the invention in an amount sufficient to
produce the desired effect, that is to say in an amount sufficient
to stabilize the oxidation-sensitive hydrophilic active principle.
Preferably, the at least one polymer or copolymer is present at a
concentration of between 0.1 and 5% by weight with respect to the
total weight of the aqueous phase and more particularly at a
concentration of between 0.1 and 2% by weight with respect to the
total weight of the aqueous phase, all concentrations within these
ranges being specifically included as if written out. A stabilizing
amount includes any amount that delays or prevents oxidation, for
example at 45.degree. C. for two months, as compared to the
composition lacking the at least one polymer or copolymer.
The compositions used according to the invention are preferably
intended for topical application to the skin and/or its superficial
body growths and therefore preferably comprise a physiologically
acceptable medium, that is to say a medium compatible with
cutaneous tissues, such as the skin, scalp, eyelashes, eyebrows,
hair, nails and mucous membranes. This physiologically acceptable
medium preferably comprises at least one aqueous phase and
optionally a physiologically acceptable organic solvent chosen, for
example, from lower alcohols comprising from 1 to 8 carbon atoms
and in particular from 1 to 6 carbon atoms, such as ethanol,
isopropanol, propanol or butanol; polyethylene glycols having from
6 to 80 ethylene oxide units; or polyols, such as propylene glycol,
isoprene glycol, butylene glycol, glycerol or sorbitol.
When the physiologically acceptable medium is an aqueous medium, it
generally has a pH which is compatible with the skin, preferably
ranging from 3 to 9 and better still from 3.5 to 7.5.
The compositions according to the invention can be provided in any
form, including any pharmaceutical dosage form used conventionally
for topical application and in particular in the form of aqueous or
aqueous/alcoholic solutions, of oil-in-water (O/W) or water-in-oil
(W/O) or multiple (triple: W/O/W or O/W/O) emulsions, of aqueous
gels or of dispersions of a fatty phase in an aqueous phase using
spherules, it being possible for these spherules to be polymeric
nanoparticles, such as nanospheres and nanocapsules, or lipid
vesicles of ionic and/or nonionic type (liposomes, niosomes or
oleosomes). These compositions can be prepared according to the
usual methods by one of ordinary skill in view of this
disclosure.
In addition, the compositions according to the invention can be
more or less fluid and can have the appearance of a white or
coloured cream, of an ointment, of a milk, of a lotion, of a serum,
of a paste or of a foam. They can optionally be applied to the skin
in the form of an aerosol. They can also be provided in a solid
form, for example in the form of a stick.
When the compositions according to the invention comprise an oily
phase, the latter preferably comprises at least one oil. It can
additionally comprise other fatty substances.
Mention may be made, as oils which can be used in the composition
of the invention, of, for example: hydrocarbonaceous oils of animal
origin, such as perhydrosqualene; hydrocarbonaceous oils of
vegetable origin, such as liquid triglycerides of fatty acids
comprising from 4 to 10 carbon atoms, such as triglycerides of
heptanoic acid or octanoic acid, or alternatively, for example,
sunflower, maize, soybean, gourd, grape seed, sesame, hazelnut,
apricot, macadamia, arara, castor or avocado oils, triglycerides of
caprylic/capric acids, such as those sold by Stearineries Dubois or
those sold under the names Miglyol 810, 812 and 818 by Dynamit
Nobel, jojoba oil, or karite butter oil; synthetic esters and
ethers, in particular of fatty acids, such as the oils of formulae
R.sup.1COOR.sup.2 and R.sup.1OR.sup.2 in which R.sup.1 represents
the residue of a fatty acid comprising from 8 to 29 carbon atoms
and R.sup.2 represents a branched or unbranched hydrocarbonaceous
chain comprising from 3 to 30 carbon atoms, such as, for example,
purcellin oil, isononyl isononanoate, isopropyl myristate,
2-ethylhexyl palmitate, 2-octyidodecyl stearate, 2-octyldodecyl
erucate or isostearyl isostearate; hydroxylated esters, such as
isostearyl lactate, octyl hydroxystearate, octyldodecyl
hydroxystearate, diisostearyl malate, triisocetyl citrate or
heptanoates, octanoates or decanoates of fatty alcohols; polyol
esters, such as propylene glycol dioctanoate, neopentyl glycol
diheptanoate and diethylene glycol diisononanoate; and
pentaerythritol esters, such as pentaerythrityl tetraisostearate;
linear or branched hydrocarbons of mineral or synthetic origin,
such as volatile or nonvolatile liquid paraffins and their
derivatives, liquid petrolatum, polydecenes or hydrogenated
polyisobutene, such as parleam oil; fatty alcohols having from 8 to
26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their
mixture (cetearyl alcohol), octyldodecanol, 2-butyloctanol,
2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl
alcohol; partially hydrocarbon-comprising and/or
silicone-comprising fluorinated oils, such as those disclosed in
the document JP-A-2-295912; silicone oils, such as volatile or
nonvolatile polymethylsiloxanes (PDMS) comprising a linear or
cyclic silicone chain which are liquid or pasty at ambient
temperature, in particular cyclopolydimethylsiloxanes
(cyclomethicones), such as cyclohexasiloxane; polydimethylsiloxanes
comprising pendent alkyl, alkoxy or phenyl groups or alkyl, alkoxy
or phenyl groups at the end of the silicone chain, which groups
have from 2 to 24 carbon atoms; or phenylated silicones, such as
phenyl trimethicones, phenyl dimethicones,
phenyltrimethyl-siloxydiphenylsiloxanes, diphenyl dimethicones,
diphenylmethyldiphenyl-trisiloxanes,
(2-phenylethyl)trimethylsiloxysilicates and
polymethylphenyl-siloxanes; their mixtures.
The term "hydrocarbonaceous oil" is understood to mean, in the list
of the oils mentioned above, any oil predominantly comprising
carbon and hydrogen atoms and optionally ester, ether, fluorinated,
carboxylic acid and/or alcohol groups.
The other fatty substances which can be present in the oily phase
are, for example, fatty acids comprising from 8 to 30 carbon atoms,
such as stearic acid, lauric acid, palmitic acid and oleic acid;
waxes, such as lanolin, beeswax, carnauba or candelilla wax,
paraffin or lignite waxes or microcrystalline waxes, ceresin or
ozokerite, or synthetic waxes, such as polyethylene waxes or
Fischer-Tropsch waxes; silicone resins, such as trifluoromethyl
C.sub.1-4 alkyl dimethicone and trifluoropropyl dimethicone; and
silicone elastomers, such as the products sold under the names
"KSG" by Shin-Etsu, under the names "Trefil", "BY29" or "EPSX" by
Dow Corning or under the names "Gransil" by Grant Industries.
These fatty substances can be chosen in a way varied by a person
skilled in the art in order to prepare a composition having the
desired properties, for example of consistency or of texture.
According to a specific preferred embodiment of the invention, the
composition according to the invention is a water-in-oil (W/O) or
oil-in-water (O/W) emulsion. The proportion of the oily phase in
the emulsion can range from 5 to 80% by weight and preferably from
5 to 50% by weight with respect to the total weight of the
composition.
The invention emulsions generally preferably comprise at least one
emulsifier chosen from amphoteric, anionic, cationic or nonionic
emulsifiers, used alone or as a mixture, and optionally a
coemulsifier. The emulsifiers are appropriately chosen according to
the emulsion to be obtained (W/O or O/W). The emulsifier and the
coemulsifier are generally present in the composition in a
proportion ranging from 0.3 to 30% by weight and preferably from
0.5 to. 20% by weight with respect to the total weight of the
composition.
Mention may be made, for the W/O emulsions, for example, as
emulsifiers, of dimethicone copolyols, such as the mixture of
cyclomethicone and of dimethicone copolyol sold under the name "DC
5225 C" by Dow Corning, and alkyl dimethicone copolyols, such as
the laurylmethicone copolyol sold under the name "Dow Corning 5200
Formulation Aid" by Dow Corning and the cetyl dimethicone copolyol
sold under the name Abil EM .sub.90.sup.R by Goldschmidt. Use may
also be made, as surfactant of W/O emulsions, of a crosslinked
solid organopolysiloxane elastomer comprising at least one
oxyalkylenated group, such as those obtained according to the
procedure of Examples 3, 4 and 8 of the document U.S. Pat. No.
5,412,004 and the examples of the document U.S. Pat. No. 5,811,487,
in particular the product of Example 3 (synthetic example) of U.S.
Pat. No. 5,412,004, and such as that sold under the reference KSG
21 by Shin Etsu. Use may also be made, as emulsifier, of a
polyolefin-derived oligomer or polymer comprising a succinic
ending; the latter is preferably a polyolefin comprising an
esterified or amidated succinic ending or a salt of such a
polyolefin and in particular polyisobutylene comprising an
esterified or amidated succinic ending such as the products sold
under the names L5603 and L2721 and OS131769 by Lubrizol.
Mention may be made, for the O/W emulsions, for example, as
emulsifiers, of nonionic emulsifiers, such as esters of fatty acids
and of glycerol which are oxyalkylenated (more particularly
polyoxyethylenated); esters of fatty acids and of sorbitan which
are oxyalkylenated; esters of fatty acids which are oxyalkylenated
(oxyethylenated and/or oxypropylenated); ethers of fatty alcohols
which are oxyethylenated (oxyethylenated and/or oxypropylenated);
sugar esters, such as sucrose stearate; and their mixtures, such as
the mixture of glyceryl stearate and of PEG-40 stearate.
According to another embodiment of the invention, the invention
composition may additionally comprise at least one active principle
(in addition to and different from the oxidation-sensitive
hydrophilic active principle) chosen from desquamating agents
capable of acting either by promoting exfoliation or on the enzymes
involved in the desquamation or the decomposition of
corneodesmosomes, moisturizing agents, depigmenting or
propigmenting agents, antiglycation agents, NO-synthase inhibitors,
5.alpha.-reductase inhibitors, lysyl and/or prolyl hydroxylase
inhibitors, agents which stimulate the synthesis of dermal or
epidermal macromolecules and/or which prevent their decomposition,
agents which stimulate the proliferation of fibroblasts or
keratinocytes and/or the differentiation of keratinocytes, muscle
relaxants, antimicrobial agents, tightening agents, agents for
combating pollution or free radicals, anti-inflammatory agents,
lipolytic active principles or active principles which have a
favourable effect, directly or indirectly, on decreasing adipose
tissue, agents which act on the microcirculation, and agents which
act on the energy metabolism of cells.
The composition of the invention can also comprise adjuvants known
in the cosmetics or dermatological field, such as hydrophilic or
lipophilic gelling agents, preservatives, solvents, fragrances,
fillers, UV screening agents, bactericides, odour absorbers,
colouring materials, plant extracts or salts. The amounts of these
various adjuvants are those generally used in the field under
consideration, for example from 0.01 to 20% of the total weight of
the composition. These adjuvants, depending on their nature, can be
introduced into the fatty phase, into the aqueous phase and/or into
the lipid spherules.
Mention may be made, as fillers which can be used in the
composition of the invention, for example, of, pigments, silica
powder; talc; particles of polyamide and in particular those sold
under the name Orgasol by Atochem; polyethylene powders;
microspheres based on acrylic copolymers, such as those made of
ethylene glycol dimethacrylate/lauryl methacrylate copolymer which
are sold by Dow Corning under the name Polytrap; expanded powders,
such as hollow microspheres and in particular the microspheres sold
under the name Expancel by Kemanord Plast or under the name
Micropearl F 80 ED by Matsumoto; silicone resin microbeads, such as
those sold under the name Tospearl by Toshiba Silicone; and their
mixtures. These fillers can be present in amounts ranging from 0 to
20% by weight and preferably from 1 to 10% by weight with respect
to the total weight of the composition.
According to a preferred embodiment, the compositions in accordance
with the invention can additionally comprise at least one organic
photoprotective agent and/or at least one inorganic photoprotective
agent which is active in the UV-A and/or UV-B regions (absorbers),
and which are soluble in water or in fats or else are insoluble in
the cosmetic solvents commonly used.
The organic photoprotective agents may be chosen in particular from
anthranilates; cinnamic derivatives; dibenzoylmethane derivatives;
salicylic derivatives; camphor derivatives; triazine derivatives,
such as those disclosed in patent applications U.S. Pat. No.
4,367,390, EP 863 145, EP 517 104, EP 570 838, EP 796 851, EP 775
698, EP 878 469, EP 933 376, EP 507 691, EP 507 692, EP 790 243 and
EP 944 624; benzophenone derivatives;
.beta.,.beta.-diphenylacrylate derivatives; benzotriazole
derivatives; benzalmalonate derivatives; benzimidazole derivatives;
imidazolines; bisbenzoazolyl derivatives as disclosed in Patents EP
669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA)
derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives
as disclosed in Applications U.S. Pat. No. 5,237,071, U.S. Pat. No.
5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening
polymers and screening silicones, such as those disclosed in
particular in Application WO 93/04665; dimers derived from
.alpha.-alkylstyrene, such as those disclosed in Patent Application
DE 198 55 649; 4,4-diarylbutadienes as disclosed in Applications EP
0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133
980 and EP 133 981; and their mixtures.
By way of illustration, mention may be made, as photoprotective
agents which are active in the UV-A and/or UV-B regions, denoted
below under their INCI names, of: p-aminobenzoic acid (PABA)
derivatives, in particular PABA, ethyl PABA, ethyl dihydroxypropyl
PABA, ethylhexyl dimethyl PABA (sold in particular under the name
"Escalol 507" by ISP), glyceryl PABA or PEG-25 PABA (sold under the
name "Uvinul P25" by BASF), salicylic derivatives, in particular
homosalate (sold under the name "Eusolex HMS" by Rona/EM
Industries), ethylhexyl salicylate (sold under the name "Neo
Heliopan OS" by Haarmann and Reimer), dipropylene glycol salicylate
(sold under the name "Dipsal" by Scher), or TEA salicylate (sold
under the name "Neo Heliopan TS" by Haarmann and Reimer),
dibenzoylmethane derivatives, in particular butyl
methoxydibenzoylmethane (sold in particular under the trade name
"Parsol 1789" by Hoffmann-LaRoche), or isopropyl dibenzoylmethane,
cinnamic derivatives, in particular ethylhexyl methoxycinnamate
(sold in particular under the trade name "Parsol MCX" by
Hoffmann-LaRoche), isopropyl methoxycinnamate, isoamyl
methoxycinnamate (sold under the trade name "Neo Heliopan E 1000"
by Haarmann and Reimer), cinoxate, DEA methoxycinnamate,
diisopropyl methyl cinnamate, or glyceryl ethylhexanoate
dimethoxycinnamate, .beta.,.beta.-diphenylacrylate derivatives, in
particular octocrylene (sold in particular under the trade name
"Uvinul N539" by BASF) or etocrylene (sold in particular under the
trade name "Uvinul N35" by BASF), benzophenone, in particular
benzophenone-1 (sold under the trade name "Uvinul 400" by BASF),
benzophenone-2 (sold under the trade name "Uvinul D50" by BASF),
benzophenone-3 or oxybenzone (sold under the trade name "Uvinul
M40" by BASF), benzophenone-4 (sold under the trade name "Uvinul
MS40" by BASF), benzophenone-5, benzophenone-6 (sold under the
trade name "Helisorb 11" by Norquay), benzophenone-8 (sold under
the trade name "Spectra-Sorb UV-24" by American Cyanamid),
benzophenone-9 (sold under the trade name "Uvinul DS-49" by BASF),
benzophenone-12, or n-hexyl 2-(4-d
iethylamino-2-hydroxybenzoyl)benzoate, benzylidene camphor
derivatives, in particular 3-benzylidene camphor (manufactured
under the name "Mexoryl SD" by Chimex), 4-methylbenzylidene camphor
(sold under the name "Eusolex 6300" by Merck), benzylidene camphor
sulphonic acid (manufactured under the name "Mexoryl SL" by
Chimex), camphor benzalkonium methosulphate (manufactured under the
name "Mexoryl SO" by Chimex), terephthalylidene dicamphor sulphonic
acid (manufactured under the name "Mexoryl SX" by Chimex), or
polyacrylamidomethyl benzylidene camphor (manufactured under the
name "Mesoryl SW" by Chimex), benzimidazole derivatives, in
particular phenylbenzimidazole sulphonic acid (sold in particular
under the trade name "Eusolex 232" by Merck), or disodium phenyl
dibenzimidazole tetrasulphonate (sold under the trade name "Neo
Heliopan AP" by Haarmann and Reimer), triazine derivatives, in
particular anisotriazine (sold under the trade name "Tinosorb S" by
Ciba Specialty Chemicals), ethylhexyl triazone (sold in particular
under the trade name "Uvinul T150" by BASF), diethylhexyl butamido
triazone (sold under the trade name "Uvasorb HEB" by Sigma 3V) or
2,4,6-tris(diisobutyl 4'-amino-benzalmalonate)-s-triazine,
benzotriazole derivatives, in particular drometrizole trisiloxane
(sold under the name "Silatrizole" by Rhodia Chimie) or methylene
bisbenzotriazolyl tetramethylbutylphenol (sold in the solid form
under the trade name "Mixxim BB/100" by Fairmount Chemical or in
the micronized form in aqueous dispersion under the trade name
"Tinosorb M" by Ciba Specialty Chemicals), anthranilic derivatives,
in particular menthyl anthranilate (sold under the trade name "Neo
Heliopan MA" by Haarmann and Reimer), imidazoline derivatives, in
particular ethylhexyl dimethoxybenzylidene dioxoimidazoline
propionate, benzalmalonate derivatives, in particular
polyorganosiloxane comprising benzalmalonate functional groups
(sold under the trade name "Parsol SLX" by Hoffmann-LaRoche),
4,4-diarylbutadiene derivatives, in particular 1,1'-dicarboxy
(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, and their
mixtures.
The organic photoprotective agents which are more particularly
preferred are chosen from ethylhexyl salicylate, ethylhexyl
methoxycinnamate, octocrylene, phenylbenzimidazole sulphonic acid,
benzophenone-3, benzophenone-4, benzophenone-5, 4-methylbenzylidene
camphor, terephthalylidene dicamphor sulphonic acid, disodium
phenyl dibenzimidazole tetrasulphonate, 2,4,6-tris(diisobutyl
4'-aminobenzalmalonate)-s-triazine, anisotriazine, ethylhexyl
triazone, diethylhexyl butamido triazone, methylene
bisbenzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane,
1,1'-dicarboxy (2,2'-dimethyl-propyl)-4,4-diphenylbutadiene, and
their mixtures.
The inorganic photoprotective agents are chosen from pigments or
alternatively nanopigments (mean size of the primary particles:
generally between 5 nm and 100 nm, preferably between 10 nm and 50
nm) formed from coated or uncoated metal oxides, such as, for
example, titanium oxide (amorphous or crystalline in the rutile
and/or anatase form), iron oxide, zinc oxide, zirconium oxide or
cerium oxide nanopigments, which are all UV photoprotective agents
well known per se. Conventional coating agents are, furthermore,
alumina and/or aluminium stearate. Such nanopigments formed from
coated or uncoated metal oxides are disclosed in particular in
Patent Applications EP 518 772 and EP 518 773.
The photoprotective agents are generally present in the
compositions according to the invention in proportions ranging from
0.1 to 20% by weight with respect to the total weight of the
composition and preferably ranging from 0.2 to 15% by weight with
respect to the total weight of the composition.
The composition according to the invention can be applied to the
skin, hair, including body hair, eyelashes, nails or lips,
depending on the use for which it is intended. It can thus be used
in a cosmetic treatment process for the skin, comprising the
application of the composition according to the invention to the
skin.
In an alternative form, the composition according to the invention
can be used for the manufacture of a dermatological
preparation.
The examples which follow serve to illustrate the invention
without, however, exhibiting a limiting nature. The compounds are,
depending on the situation, cited according to chemical names or
according to CTFA (International Cosmetic Ingredient Dictionary and
Handbook) names.
EXAMPLES
Example 1
Accelerated Storage Test
The aim of this test is to study the decomposition of an
oxidation-sensitive hydrophilic active principle after storing for
two months at 45.degree. C. Various solutions were prepared and
their compositions are collated in the following table:
TABLE-US-00001 TABLE I Compositions (in Solution A water) (Control)
Solution B Solution C Solution D Ascorbic acid 15% 15% 15% 15%
Polymer 1 -- 1% -- -- Polymer 2 -- -- 1% -- Polymer 3 -- -- -- 1%
All the solutions are brought to pH 6 with 8.9 mol/l KOH. The
percentages of the polymers are given as active material. Polymer
1: Vinylpyrrolidone/vinylimidazole (50/50) copolymer sold under the
reference Luvitec VPI 55K72W of BASF (Weight-average molecular mass
1.2 .times. 10.sup.6). Polymer 2: Vinylpyrrolidone/vinylimidazole
(50/50) copolymer sold under the reference Luvitec VPI 55K18P of
BASF (Weight-average molecular mass 10000). Polymer 3:
Polyvinylpyrrolidone sold under the reference Kollidon 12PF of BASF
(Weight-average molecular mass 3000).
The degree of decomposition measured is given by the ratio:
(C.sub.0-C.sub.2 months)/C.sub.0 with C.sub.0 concentration of
ascorbic acid at t=0 and C.sub.2 months the concentration of
ascorbic acid at t=2 months, under the conditions indicated in the
above table. The concentration of ascorbic acid is determined by
the HPLC technique (LaChrom Merck system). The analytical
conditions are as follows: Column: Lichrosphere100 RP18 (250 mm)
Eluent: 0.1M phosphate buffer, pH 2.1 Flow rate: 1 ml/min Detection
at 257 nm Dilution of the sample such that the concentration of
ascorbic acid is between 0.05 and 1 mg/ml.
The results obtained are collated in the following Table II:
TABLE-US-00002 TABLE II Degree of decomposition after 2 months at
45.degree. C. (in %) under air, amber glass under nitrogen,
aluminium bottle flask Solution A 43 19.4 Solution B 10.8 1
Solution C 23.4 4.5 Solution D 35.8 15.7
It is found, from Table II, that the stability of ascorbic acid is
improved in the presence of Polymer 1 and Polymer 2 of the
invention, even in the presence of atmospheric oxygen, in
comparison with the control. It is also found that the
N-vinylpyrrolidone homopolymer alone is not sufficient to
effectively stabilize the ascorbic acid solution. Preferred
invention results for this test using ascorbic acid as above are 30
or below in air, including 25, 20, 15, 10, 5, etc. and less than or
equal to 10 in nitrogen including 8, 5, etc. General degrees of
decomposition after two months in air at 45.degree. C. preferably
are less than or equal to 25%, including 20, 15, 10, 5%, etc. and
all intervening values as if written out. As the polymers mentioned
are hydrophilic, it will be sufficient to add them to an aqueous
ascorbic acid solution to stabilize the ascorbic acid.
Example 2
Fluid W/O Emulsion
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00003 Phase A: Cetyl dimethicone copolyol 1.5 g
Polyglyceryl-4 isostearate 0.5 g Squalene 3.7 g Isohexadecane 7.95
g Polydimethylsiloxane 4 g Apricot oil 2.25 g Phase B: Ascorbic
acid 5 g 50% Potassium hydroxide 3 g
Vinylpyrrolidone/vinylimidazole copolymer 3.3 g (Luvitec VPI55K72W
from BASF) Glycerol 5 g Preservatives 0.4 g Water 60.4 g Nylon-12
powder 3 g
A fluid is obtained which is soft on application, with good
stability of the ascorbic acid.
Example 3
Fluid W/O Emulsion for the Radiance of the Complexion
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00004 Phase A: Ethanoldiethonium polyisobutenyl triethyl-
2 g aminosuccinate (and) diethyl ethanolamine (Lubrizol LZ 5603)
Isohexadecane 8 g Hydrogenated polyisobutylene 3.7 g Apricot oil
6.4 g Phase B: Ascorbic acid 5 g 50% Potassium hydroxide 3 g
Vinylpyrrolidone/vinylimidazole copolymer 3.3 g (Luvitec VPI55K72W
from BASF) Glycerol 5 g Preservatives 0.4 g Water 61.2 g Nylon-12
powder 2 g
A care cream for the skin is obtained, which cream is soft on
application, with good stability of the ascorbic acid.
Example 4
Fluid W/O Emulsion
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00005 Phase A: Isostearyl diglyceryl succinate 4 g
Octyldodecanol 4 g Apricot oil 8 g Cyclomethicone 12 g Synthetic
ceramide 0.1 g Silicone gum 6 g Phase B: Ascorbic acid 5 g 50%
Potassium hydroxide 3.07 g Vinylpyrrolidone/vinylimidazole
copolymer 1 g (Luvitec VPI55K72W from BASF) Glycerol 2 g Aluminium
starch octenylsuccinate 0.3 g Preservatives 0.5 g Demineralized
water 54.03 g
A care cream for the skin is obtained, which cream is pliable and
soft on application, with good stability of the ascorbic acid.
Example 5
O/W Face Cream
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00006 Phase A: Glyceryl stearate and PEG-100 stearate 2.1
g Polysorbate 60 0.9 g Cetyl alcohol 2.6 g Hydrogenated
polyisobutene 12 g Cyclomethicone 8 g Phase B: Demineralized water
59.23 g Glycerol 2 g Ascorbic acid 5 g 50% Potassium hydroxide 3.07
g Vinylpyrrolidone/vinylimidazole copolymer 1 g (Luvitec VPI55K72W
from BASF) Xanthan gum 0.1 g Carbomer 0.4 g Phase C:
Triethanolamine 0.3 g Demineralized water 3 g Preservative 0.3
g
A care cream for the skin is obtained, which cream is rich and soft
on application, with good stability of the ascorbic acid.
Example 6
W/O/W Multiple Emulsion
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00007 Primary emulsion Phase A: Polyglyceryl-4 isostearate
and 3.5 g cetyl dimethicone copolyol and hexyl laurate
Cyclopentasiloxane 16.5 g Dimethicone (silicone gum) 4 g Phase B:
Demineralized water 46.27 g Ascorbic acid 15 g 50% Potassium
hydroxide 9.33 g Vinylpyrrolidone/vinylimidazole copolymer 3.3 g
(Luvitec VPI55K72W from BASF) Glycerol 2 g Pentasodium
ethylenediaminetetramethylene- 0.1 g phosphonate (33% aqueous
solution) Multiple emulsion Phase A: Primary emulsion 20 g
Cyclopentasiloxane 5 g Apricot kernel oil 5 g Phase B: Ammonium
polyacryloyldimethyl taurate 0.4 g Acrylates/C.sub.10-30 alkyl
acrylate crosspolymer 0.6 g Demineralized water 35.7 g Preservative
1 g Phase C: Demineralized water 5.7 g Triethanolamine 0.7 g Phase
D: Ammonium polyacryloyldimethyl taurate 0.6 g Demineralized water
25.3 g
A white and fresh cream is obtained which confers good stability on
ascorbic acid and is capable of being applied to the skin.
Example 7
Ascorbic Acid Microcapsules
A 15% by weight aqueous ascorbic acid solution, at pH 6, comprising
3.3 g of vinylpyrrolidone/vinylimidazole copolymer (Luvitec
VPI55K72W.RTM. from BASF), is prepared. 5 ml of this solution are
emulsified in 50 ml of methylene chloride comprising 5% of
cellulose acetate-propionate (CAP-482-0.5.RTM., Eastman Chemical)
for 5 min using a homogenizer of rotor-stator type while
maintaining the temperature below 25.degree. C. This primary
emulsion is subsequently dispersed in 500 ml of an aqueous solution
comprising 1% of polyvinyl alcohol (Airvol 203.RTM., Air Products)
and 7% of sodium chloride for 20 min at ambient temperature using a
Moritz disperser.
The solvent of the suspension is subsequently evaporated for 5
hours at 40.degree. C. at a pressure of 75 kPa using a rotary
evaporator (Buchi B-480).
A dispersion of microcapsules, the mean size of which is 20 .mu.m,
with a degree of encapsulation of 85% and a manufacturing yield of
100%, is obtained.
Example 8
Day Cream Comprising the Microcapsules According to Example 7
TABLE-US-00008 Phase A: Cetyl alcohol 4 g Sorbitan tristearate 0.9
g Polyethylene glycol stearate 2 g Glyceryl stearate 3 g Myristyl
myristate 2 g Octyl palmitate 4.5 g Parsol MCX .RTM. (sold by 3 g
Hoffmann-LaRoche) Cyclopentasiloxane 5 g Preservative 0.1 g Phase
B: Demineralized water 60.3 g Preservative 0.15 g Sequestering
agent 0.05 g Phase C: Powder formed from microcapsules 15 g
according to Example 7
Example 9
W/O Cream
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00009 Water 21.05 g Phenoxyethanol 0.5 g Methyl paraben
0.3 g Water 71.3 g Kojic acid 1 g Vinylpyrrolidone/vinylimidazole
copolymer 0.5 g Biosaccharide Gum-1 2 g Polysorbate 20 1 g
Cyclopentasiloxane (and) 10 g dimethicone copolyol
Cyclopentasiloxane 8 g Dimethicone (and) dimethicone/vinyl 3 g
dimethicone crosspolymer Tocopherol (and) glycine soya (soybean)
oil 0.4 g Polyacrylamide (and) C.sub.13-14 2 g isoparaffin (and)
laureth- 7
A care cream for the skin is obtained, with good stability of the
ascorbic acid.
Example 10
W/O Gel
The following composition is prepared in a way conventional to a
person skilled in the art.
TABLE-US-00010 Cyclopentasiloxane (and) dimethicone 17.5 g copolyol
Sodium methylparaben 0.3 g Chlorphenesin 0.25 g Water 81.2 g
Phloroglucinol 0.5 g Vinylpyrrolidone/vinylimidazole copolymer 0.25
g
A gel for the skin is obtained, with good stability of the ascorbic
acid.
The above description of the invention, as explained and
illustrated by Examples, enables one of ordinary skill in the art
to make and use a composition comprising, preferably in a
physiologically acceptable medium comprising an aqueous phase, at
least one oxidation-sensitive hydrophilic active principle and at
least one non-crosslinked N-vinylimidazole polymer or copolymer,
the active principle and the polymer or copolymer both being in the
aqueous phase. In addition, one of ordinary skill is enabled to use
a non-crosslinked N-vinylimidazole polymer or copolymer to
stabilize an oxidation-sensitive hydrophilic active principle in an
aqueous medium.
French patent application 0115375 is incorporated herein by
reference, as are all documents, references, texts, standards,
applications, patents, etc., mentioned above.
Also incorporated herein by reference are the following U.S.
applications, all filed Nov. 27, 2002, where the present
application is listed for information only: U.S. Ser. No.
10/304,860 U.S. Ser. No. 10/304,861 U.S. Ser. No. 10/305,115 U.S.
Ser. No. 10/304,862 U.S. Ser. No. 10/305,114
* * * * *